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Electronic supplementary information

Spiro[fluorene-9,9'-xanthene]-based hole transporting materials for efficient

perovskite solar cells with enhanced stability

Kuan Liu,ab Yuehan Yao,a Jiayu Wang,a Lifeng Zhu,b Mingli Sun,c Baoyi Ren,d Linghai Xie,c

Yanhong Luo,b Qingbo Meng*b and Xiaowei Zhan*a

a Department of Materials Science and Engineering, College of Engineering, Key Laboratory of

Polymer Chemistry and Physics of Ministry of Education, Peking University, Beijing 100871, China.

E-mail: xwzhan@pku.edu.cnb CAS Key Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy Materials

and Devices, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China. E-mail:

qbmeng@iphy.ac.cnc Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced

Materials, National Synergistic Innovation Center for Advanced Materials, Nanjing University of

Posts & Telecommunications, Nanjing, Jiangsu 210023, Chinad College of Applied Chemistry, Shenyang University of Chemical Technology, Shenyang, Liaoning

110142, China

Electronic Supplementary Material (ESI) for Materials Chemistry Frontiers.This journal is © the Partner Organisations 2016

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O

O

+

BrBr

BrBr

Br

BrBr

Br

N

MeO OMe

BO O

Pd(PPh3)4, K2CO3 (aq)

toluene, reflux

ON

OMe

MeO N

NN

OMe

OMeOMe

OMe

OMeMeO

O

N

N

N

N

OMe

MeO

MeO

OMe

OMe

OMe

OMe

OMe

O

O

BrBr

BrBr

Br

BrBr

Br

+NH

OMeMeOPd2dba3, P(t-Bu)3, t-BuONa

toluene, reflux

O

NN

N N

O

N N

N N

OMe

OMe

OMe

OMeOMe

MeO

MeO

OMe

OMe

MeO

MeO

OMe OMe

OMe

OMe

OMe

SFX-1

SFX-2

SFX-1

SFX-2

mp-SFX-3PA

mm-SFX-3PA

mm-SFX-2PA

mp-SFX-2PA

3PA-B

2PA

Scheme S1. Synthesis routes of four HTMs.

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Fig S1. The optimized geometries, electron distribution of HOMO, HOMO-1 and LUMO of

different HTMs.

Fig S2. TGA curves of different HTMs.

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Fig S3. Normalized UV-vis absorption spectra of different HTMs in DCM solution.

Fig S4. J-V characteristics of hole-only devices based on doped HTMs under dark.

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Fig S5. Effect of doped mp-SFX-2PA thickness on the performance of MAPbI3 based PSCs.

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Fig S6. (a) J-V curve of PSC based on doped spiro-OMeTAD, measured under AM 1.5G

illumination, 100 mW cm-2. (b) EQE spectrum as a function of the wavelength of monochromatic

light. (c) Steady-state current density and power output measured at the maximum power point (817

mV).

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Fig S7. Statistical distribution histogram of PCEs of MAPbI3 PSCs with dopant (20 devices for each

case).

Fig S8. J-V curves of MAPbI3 based devices with doped mp-SFX-2PA: (a) under different scanning

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directions with 0.1 V/s rate, (b) under different scanning rate of reverse scanning. J-V curves of

doped spiro-OMeTAD based devices: (c) under different scanning directions with 0.1 V/s rate, (d)

under different scanning rate of reverse scanning.

Fig S9. (a) Steady-state current density and power output for the (FAPbI3)0.85(MAPbBr3)0.15 based

PSCs using doped mp-SFX-2PA and doped spiro-OMeTAD measured at the maximum power point.

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J-V curves of the (FAPbI3)0.85(MAPbBr3)0.15 based PSCs employing (b) doped mp-SFX-2PA and (c)

doped spiro-OMeTAD under different scanning directions with 0.1 V/s rate.

Fig S10. Normalized hole mobility as a function of time for the MAPbI3 devices based on doped mp-

SFX-2PA and doped spiro-OMeTAD, stored under ambient condition (20 ± 5 oC, 15 ± 5 % relative

humidity).

Table S1. Calculated LUMO+1, LUMO, HOMO and HOMO-1 energy levels

mp-SFX-

3PA

mm-SFX-

3PA

mp-SFX-

2PA

mm-SFX-

2PA

spiro-

OMeTAD

LUMO+1 -0.67 -0.66 -0.36 -0.44 -0.65

LUMO -1.08 -1.10 -0.65 -0.72 -0.67

HOMO -4.47 -4.47 -4.27 -4.32 -4.27

HOMO-1 -4.57 -4.48 -4.58 -4.37 -4.29

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Table S2. Photovoltaic parameters of the MAPbI3 based PSCs with different thickness of doped mp-

SFX-2PA

Thickness of mp-

SFX-2PA (nm)JSC (mA cm-2) VOC (mV) FF (%) PCE (%)

130 20.24 1001 75.90 15.38

100 20.75 1008 77.53 16.22

80 19.33 997.0 78.00 15.03

65 18.23 986.0 77.12 13.86